Azo dyestuffs and fiber dyed therewith



Patented Jan. 23, 1934 T A T E Fries.

AZO DYESTUFFS AND FKBER DYED THEREVVITH No Drawing. Application May 4, 1932, Serial No. 609,266, and in Germany May 31, 1931 Claims.

The present invention relates to new azo dyestuffs and to fiber dyed therewith, more particularly it relates to azo dyestuffs of the general formula:

wherein m means the number 1 or 2, Y stands for an alkoxy or alkylthio group, R1 for a radical of the benzene, naphthalene, diphenyl or anthrai quinone series, and R for a radical of the benzene,

naphthalene or diphenyl series.

In the pertaining art azo dyestuffs have been described which are obtainable by combining a diazo compound with a 2.3-hydroxynaphthoic 2o acid arylide substituted in the arylide radical by one or more alkoxy groups. However, dyestuifs made from 2.3-hydroxynaphthoic acid arylides substituted by such groups in the nucleus of the 2.3-hydroxynaphthoic acid radical are not known.

In View of the lack of knowledge of the behavior of 2.3-hydroxynaphthoic acid arylides substituted by alkoxy groups in the 2.3-hydroxynaphthoic acid radical, nothing can be foretold as to the effect which may be produced by such substituents on the properties of the dyestufis formed from these arylides.

We have found that new azo dyestuffs are obtainable by coupling a suitable diazo-compound with an arylide of a 6-alkoXy-2/3-hydroxynaphthoic acid.

It is surprising that the shades of the dyestuifs obtainable by using a S-alkox -2.3-hydroxynaphthoic acid arylide as the azo-component are situated considerably nearer to the to blue of the spectrum than those of the dyestuffs obtained by means of the known corresponding 2.3-hydroxynaphthoic acid arylides which do not contain an alkoxy group in the 6-position of the naphthalene nucleus. Such an extension and variation of the color scale is of particular industrial advantage.

Furthermore, we have found that new azo dyestuffs are also made by coupling a suitable diazocompound with an arylide of a 6-a1ky1thio-2.3

hydroxynaphthoic acid, or with an arylide of a 5-, '7- or 8-alkoxy-2.3-hydroxynaphthoic acid or of a 5-, 7- or 8-alkylthio-2.3-hydroxynaphthoic acid.

By using the 6-alkylthio-2.3-hydroxynaphthoic acid arylides, the shades of the dyestuffs obtained are likewise displaced to the blue side of the spectrum. In the case of the dyestuffs obtainable by using as azo components 2.3-hydroxynaphthoic acid arylides which contain an alkoxyor alkylthio group in the 5-, '7- or 8-position of 0 the naphthalene'nucleus, the shades are not so much altered. The shades of the dyestuffs obtainable from 7-alkoxy-23-hydroxynaphthoic acid arylides are not at all, or only somewhat, displaced to the yellow side of the spectrum.

The dyestufis can be made in the usual manner by producing them in substance or on the fiber or on any of the usual substrata adapted for the production of lakes.

If the dyestuiis are produced on the fiber, it is essential that the components, the diazo compound as well as the arylide compound, contain no substituents known to render azo dyestuffs made from 2.3-hydroxynaphthoic acid arylides soluble in water or alkalies and tending to depreciate the fastness of the dyeings to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid groups.

The following examples serve to illustrate the invention the parts being by weight, unless other- 30 wise stated:

(1) 50 grams of cotton yarn are impregnated with a solution containing 6 grams of 6-methoxy-2-hydroxynaphtha- Iene-B-carboxylic acid anilide, 12 cc. of sodium Turkey red oil of 50% strength, 40 cc. of 2N-caustic soda solution,

6 cc. of formaldehyde of 40% strength,

G1 10o i -Q l By using a diazo compound of 4-amino-L3- 11o (2) 6 grams of G-methoxy 2 hydroxynaphthalene-3-carboxylic acid 4 methyl-1-anilide are mixed with 12 cc. of sodium Turkey red oil and cc. of ZN-caustic soda solution; the whole is dissolved by addition of hot water,

12 cc. of caustic soda solution of 40 B. and

6 cc. of formaldehyde solution of 40% strength are added, and the Whole is made up to grams of cotton yarn are impregnated with this solution, squeezed and developed by means of a solution containing, per liter, the diazo compound made from 3.2 grams of 2.5-dichloroaniline, and feebly acid with acetic acid. When the coupling is finished, the material is rinsed and soaped in a boiling soap bath. There is obtained abright ruby-red dyeing.

The dyestuff has the following formula:

Abordeaux-red dyeing is obtained by impregnating the fiber with a solution of G-methylthio- 2-hydroxynaphthalene-3-carboxylic acid anilide or 6 methylthio 2 hydroXynaphthalene-3-carboxylie acid-orthmtoluidide and developing the dyestuif in the same manner with a diazo-solution: of 2.5-dichloroaniline. By using the same diazo compound and 7 methoxy2-hydroxynaphthalene-3-carboxylic acid-4-methyl-l-anilide,'a scarlet dyeing is obtained.

(3) "Cotton yarn which has been prepared in a suitable manner is impregnated with a solution containing moo 2 grams of G-methoXy-Z-hydroxynaphthalene- 3-carboxylic acid 2' methoXy-1- anilide,"

4 cc. of sodium Turkey red oil of 50% strength, and 4 cc. of caustic soda solution of 34 B.

' per liter and squeezed. Thereupon, the dyestuif is developed in a diazo-solution which has been neutralized by means of sodium bicarbonate and contains per liter the diazo compound of 3 grams of l-amino 4 benzoylarnino-Z.5-diethoXybenzene. rinsed and soaped.

There is obtained a bluish-green dyeing of good properties of fastness.

The dyestuif has the following formula:

grams of Y-methylthio 2 hydroxynaphthalene 3 carboxylic acid-2-methoxy-\ 1 anilide (melting at 164 C.) are dissolved in of alcohol,

of water and of caustic 38 B.

12 cc. 1.5cc. 1.5cc.

soda solution of ill This solution is introduced into a solution of 5 cc. of Turkey redoil of 50% strength, 5 cc. of caustic soda solution of 38 B., and

975 cc. of Water.

50 grams of cotton yarn are treated with this grounding liquor for half-an-hour; thereupon, the yarn is squeezed or hydroextractedand developed with a diazo-solution, feebly acid with acetic acid and prepared in the-usual mannerby diazotizing 2 grams of 4-chloro-2-amino-1- toluene hydrochloride, adding sodium acetate until the diazo-solution is neutral to Congo paper, then adding 25 grams of dissolved sodium chloride and making up the Whole to 1 liter. Whenthe development is completed, the material is well rinsed, soaped in a boiling soap bath and dried. A bright red dyeing of good fastness properties is thus obtained.

The dyestuff has the following formula:

By developing in the same manner with a diazoii solution from meta-chloraniline, there is obtained a somewhat dull red dyeing, and by developing with a diazo-solution from 2.5-dichloraniline, there is obtained a brownish-red dyeing.

By impregnating the fiber in an analogous" manner with 7-methylthio-2-hydroxynaphthalene-3-carboxylic acid-2-methy1-4-methoxy-l'- anilide (melting at 214 C.) and developing the dyestuif with diazotized e-chloro-z-aminodtoluene, there is obtained a yellowish-red dyeing; by developing with diazotized meta-chloraniline or diazotized 2.5-dichloraniiine more yellowishred dyeings are obtained.

(5) Cotton yarn which has been prepared in a suitable manner is impregnated with a solution containing 2 grams of G-methylthio-2-hydroxynaphthalene-3-carboxylic acid anilide,

4 cc. of sodium Turkey red oil of 50% strength,

and

4 cc. of caustic soda solution of 34 Be.

per liter and squeezed. Thereupon, the dyestuff is developed in a diazo-solution, which has been neutralized by means of sodium bicarbonate and contains per liter the diazo-compound of 3 grams of 1 amino-4-benzoy1a1nino-25-diethoxy-benzene, rinsed and soaped.

There is obtained a greenish-blue dyeing of good properties of fastness.

The dyestufi has the following formula:

sCzO OCzH5 I /OH (6) 293 parts of 6-methoxy-2-hydroxynaphthalene-3 -carboxylic acid anilide are made into a paste with 500 parts of acetone, which paste is dissolved by addition of 200 parts of caustic soda solution of 40 B. and 9000 parts of water. To thissolution, there is run a diazosolution which is prepared in the usual manner from 162 parts of 2.5-dichloraniline. The dyestuii" obtained is filtered by suction and forms a bluish-red powder.

The following table indicates a munber of dyestuffs obtainable according to the present invention, but it is not intended to limit the invention to the dyestuffs mentioned therein.

Diazotizing component Coupling component Shade 1-amino-4-benzoylamino-25dirnethoxybenzene 4-amino-4-methoxydiphenylamine l-aininoi-benzoylaminc-2.5-diethoxybenzene 1-amin0-i-benzoy1an1ino-2iS-(limethoXybenZene 4-an1ino-4-Inethoxydiphenylamine 1-an1ino-4'benzoy1an1ino-2.5-diethoxybenzene 25 diohloraniline 2.3-dichloro-4-methyl-l-aminobenzene 2-chlor-5-methoxy-4-benzoylamino-laminob enzene 2-phenoxy-5-chloro-l-aminobenzene 4-ch1oro-2-nitro-l-aminobenzene. 5-nitro-2-methy1-1-aminobenzene 4-methy1-2-nitro-1-aminobenzene--. 2"-dimethy1-4-amino-azobenzcne.

5-chloro-2-n1ethoxy-4-benzoylamino-l-amino-benzene methylthio 2 hydroxynaphthalene 3 Blue carboxylic acid-anilide Greenish-blue .do methylthio 2 hydroxynaphthalene 3 Blu carboxylio acid-2-methy1-l-anil1de niethylthio 2 hydroxynaphth Do.

carboxylic acid-2-methoxy-l -anilide d Reddish-blue Blue - methoxy 2 hydroxynaphthalene 3 car Bluish-red boxylic acid-anilide Clear bluish-red Garnet Dark current-brown Bluish-red Garnet Bluish-red Yellowish-garnet Blackish-currant Dark violet-blue 4-methoxy-4-aminodiphenylaniine Dark blue 4-nitro 2.5-dimethoxy-4-aminoazobenzene Black 2-methyl-5methoxy-4-amino-4 (-p-aminophenylamino)- Greenish-black azobenzene 22 2.5-dioh1oranil1ne ii 6 ethoxy 2 -hydroxynaphtha1ene 3 carboxyl- Bluish-red ic acid-anilirle 23 D0 6-isopropyloxy-2-hydroxynaphthalene-B-carbox- Do.

ylic aoid-anilide 24 Do o-n-butyloxy-2-hydroxynaphthalene-3-carboxyl- Do.

ic acid-anilide 25 Do 6-isoamyloxy-2 hydroxynaphthalene-3-carboxy1- D0.

ic acid-ani1ide 26 Do 6-sec.-octyloxy-2-hydroxynaphthelene-3 -carbox- Do.

ylic acid-anilide 27 4 -methoxy-4-am1nod1pheny1-am1ne 0 6 etliioxy -12dhydroxynaphthalene 3 carboxylic Blue am -am 1 e 28 Do 6-isopropyloxy-2-hydroxynaphthalene-3-carbox- Do.

ylic acid-anilide 29 Do 6-n-butyloxy-2-hydroxymaphthalene-B-carboxyl- Do 1e acid-anilide 30 Do G-isoamyloxy-2-hydroxynaphtha1ene-3-carboxyl- Do.

ic acid-anilide 31 Do 6 sec. octyloxy 2 hydroxynaphthalene 3 Do.

carboxylie acid-anilide 32 m-chloranilme 6 methoxy 2 hydroxynaphthalene 3 car- Bordeaux boxylic acid-25-dimethoxy-1-anilide 33 4-ch1oto-2-n1ethyl-l-aminobenzene o Do. 34 Do. 35 7 Do. 36 Ruby-rod 37 Garnet 38 Do. 39 Z-nitraniline Do. 40 2-methy1-4-nitro-1-aminobenzen Bluish-garnet 41 4-methy1-2-nitro-l-aminobenzene Currant 42 4-ch10r0 2-nitro-1-aminobenzene- Do. 43 2methoxy-4-nitro-l-aminobenzene Bluish-ourrant 44 4-methoxy- -nitro-l-aininobenzene l Black-vio1et 45 2.5-dimethoxy-4-benzoylamino-1-aminobenzene Reddish-blue 46 4-methoxy-4-amincdiphenylamine Covered navy blue 47 4-nitro-2.5-dimethoxy-4-aminoazobenzene. o do Bluish-black 43 2.5-dich1orani1ine .l G nicthoxy 2 -hydroxynaphthalene 3 Ruby-red carboxylic acid-2 5-dimethyl-l -ani1ide 49 5-chloro-2-n1ethyl-l-aminobenzene do Vivid bordeaux 50 o-chloranilme do Red Coupling component Shade Bordeaux-garnet 51 o-nitraniline 6 methoxy 2 hydroxynaphthalene 3 carboxylic acid 2' 5'-dilnethyl-1-anilide 80 52 a-aminoanthraquinone d Garnet 53' 4-ch1oro-2-nitro-l-amin0benzene d0 Currant 54 2-methyl-4-nitro-1-aminobenzene do Do. 55 4-nitraniline do Do. 56 4-methoXy-2-nitrani1ine -dO Violet-black 57 2-Ineth0Xy-4-nitraniliue .dO Black-violet 58 2.4-dimethyl-2-nitro-5-methoxy-aminoazobenzene d0 Very, deep violetbrown. 85 59 4-methoxy-4-amino-diphenylamlne d0 Greenish-navy blue 60 2.5-dimethoxy-4-benzoylamino-l-aminobenzene do Reddish-blue 61 o-dianisidine Greenish-navy blue 62v o-phenitidine-azo-wnaphthylamine Greenish-black 63 4.4-diamino diphenylamine Blacbblue 64 2-Inethoxy-4-amino-4-dimethylaminoazobcnzene Greenish-blaek 65 3-methoxy-4-amino-4-dimethylaminoazobenzene Do. 90 66 3-methoXy-4-aminodiphenylamme Do.

10 acid-a-naphthylamide 67 Do 6-Iuethoxy-2-hydroxy-naphthalene-3=carbox- Do.

ylic acid-B-naphthylamide 68 pmitmniline 6 methoxy 2 hydroxynaphthalene 3 ear- Bordeaux-current boxylic acid-2-chloro-l-anilide 69 Do 6 methoxy 2 hydroxynaphthalene 3 car- Brownish-red 95 boxylic acid-3-chloro-l-ani1ide 70 Do 6 methoxy 2 hydroxynaphthalene 3 car- Currant boxylic acid-4J-ch1oro-1-anilide 71 o-chloraniline 6 methoxy 2 hydroxynaphthalene 3 car- Bluish-red boxylic acid-4-nitro-l-anilide 72 2.5-diethoxy-4-benzoylamino-l-aminobenzene 6 methoxy 2 hydroxynaphthalene 3 car- Navy blue boxylic acid-3-nitro-1-anilide 73 2-methoxy-4-nitroaniline 6 methoxy 2 hydroxynaphthalene 3 car- Violet 100 boxylic acid-3 -nitro-4 -ethoxy-1-ani1ide 74 o-dianisidine 6 methoxy 2 hydroxynaphthalene 3 car- Navy blue boxylic acid-4-phenylamino-1-anilide 75 2-methoxy-4-nitroani1ine 6 methoxy 2 hydroxynaphthalene 3 car- Violet boxylic acid-4'-phenyl-1-ani1ide 76 a-naphthylamine 6 methoxy 2 hydroxynaphthalene 3 car- Black-violet boxylic acid-B-naphthylamide 1 77 a-aminoanthraquinone di (6 methoxy 2 hydroxynaphthalene 3 Garnet 78 2.5-diethoxy-4-benzoyl-amino-l-aminobenzene Black-violet 79 4'-methoxy-4-aminodiphenylamine Bluish-black 80 as.-m-xy1idine Garnet 81 2-methoxy-l-amin0-5-su1fonic acid-diethylamide Dark bordeaux 82 2.4 dimethyl 2 nitro- 5 methoxy 4 aminoazoben- Dark brown zene 11G 83 4-nitro-2.5-dimethoXyA-ammoazobenzene do Black-brown 84 4-chloro-2-methyl-1a1uinobenzene di (fi-methoxy 2 hydroxy naphthalene 3 Garnet carboxylic acid-)p-phenylenediamine 85 2methoxy-4-nitro-l-aminobenzene do Currant 86 4-nitm-2.5-dirueth0xy-4-amin0azobenzene ,do Black 87 4-nitraniline .d0 Reddish-brown 88 4-methyl-2-nitro-1-aminobenzene di (6 methoxy 2- hydroxy naphthalene 3 Garnet 115 carboxylic acid-) m-phenylenediamine 89 2-n1ethoxy-5-nitro-Leminobenzene .do Bordeaux 90 z-chloro-l-aminobenzene n do Very bluish-red 91 4-methoxy-4-amino-diphenylamme do Greenish-navy blue 92 2.4 dimethyl- 2 nitro 5 methoxy 4 aminoazoi do Bluish-black benzene 93 4-nitro-l-aminobenzene d0 Garnet 94 4-chloro-2-methyl-l-aminobenzene di (fi-methoxy 2 hydroxynaphthalene 3 Bordeaux 12@ carboxylic acid-)4l4-diaminodiphenylether 95 amethoxy-A-nitro-l-aminobenzene d Garnet 96 a-aminoanthraquinone Bordeaux 97 2.5-dichloraniline Do. 98 23-diinethyl-4-aminoazobenzene Currant We claim:

1. The azo dyestuifs of the following general formula:

wherein a: means the number 1 or 2, Y stands for an alkoxy or alkylthio group, R1 for a radical of'the benzene, naphthalene, diphenyl or anthraof the benzene, yielding, when various shades.

3. The azo dyestuffs of the following general formula:

wherein a: means the number 1 or 2, Y stands for an alkoxy or alkylthio group, R1 for a radical of the benzene, naphthalene, diphenyl or anthraquinone series, and R for a radical of the benzene, naphthalene or diphenyl series, yielding,

when produced on the fiber, dyeings of various shades.

2. The azo dyestuffs of the following general formula:

wherein at means the number 1 or 2, Y stands for an alkoxy group, R1 for a radical of the benzene, naphthalene, diphenyl or anthraquinone duced on the fiber, dyeings of Various shades.

4. The azo dyestuffs of the following general formula:

wherein Y stands for an alkoxy group, R1 for a radical of the benzene, naphthalene, diphenyl or anthraquinone series, and R for a radical of the benzene, naphthalene or diphenyl series, yielding, when produced on the fiber, dyeings of various shades.

5. The azo dyestuffs of the following general formula:

wherein R1 stands for a radical of the benzene, naphthalene, diphenyl or anthraquinone series, and R for a radical of the benzene, naphthalene or diphenyl series, yielding, when produced on the fiber, dyeings of various shades.

6. The azo dyestuffs of the following general formula:

wherein R1 stands for a radical of the benzene series, and R for a radical of the benzene, naphthalene or diphenyl series, yielding, when produced on the fiber, dyeings of various shades.

'7. The azo dyestuffs of the following general formula:

wherein R and R1 stand for radicals of the benzene series, yielding when produced on the fiber, dyeings of various shades.

8. Fiber dyed with the azo dyestuffs as claimed in claim 1.

9. Fiber dyed with the azo dyestuffs as claimed in claim 2.

10. Fiber dyed with the azo dyestuffs as claimed in claim 3.

yielding, when produced on the fiber, a bluishgarnet dyeing.

16. The azo dyestuff of the following formula:

OH E1 (JO-NHOOHa yielding, when produced on the fiber, a bright ruby-red dyeing.

17. The azo dyestuff of the following formula:

moo

HaCO

yielding, when produced on the fiber, a bluishgreen dyeing.

18. Fiber dyed with the azo-dyestuif as claimed in claim 15.

19. Fiber dyed with the azo dyestufi as claimed in claim 16.

20. Fiber dyed with the azo dyestuff as claimed in claim 17.

moo

ARTHUR ZITSCHER. HEINRICH MORSCHEL. WILHELM LUCE. 

